CN103945986B

CN103945986B - The processing method of used fixed abrasive wire saw cutting fluid composite

Info

Publication number: CN103945986B
Application number: CN201280055989.5A
Authority: CN
Inventors: 土井康广; 樫原荣二; 铃木清史
Original assignee: Kao Corp; Palace Chemical Co Ltd
Current assignee: Kao Corp; Palace Chemical Co Ltd
Priority date: 2011-11-15
Filing date: 2012-11-15
Publication date: 2017-03-08
Anticipated expiration: 2032-11-15
Also published as: WO2013073618A1; JPWO2013073618A1; JP5988995B2; CN103945986A

Abstract

A kind of used fixed abrasive wire saw cutting fluid composite is (hreinafter referred to as " cutting fluid composite ".) processing method, wherein, contain specific polyether compound (composition A) 25～75 weight %, specific surfactant (composition B) 1～9 weight %, He Shui (composition C) using front cutting fluid composite, the cloud point of cutting fluid composite is 30～80 DEG C, and the powder removal step at least removing cutting powder from oil extraction liquid includes：First operation, oil extraction liquid is heated to the temperature of more than the cloud point of cutting fluid composite, the lower floor being separated into the upper strata with polyether compound as main component and wanting composition based on water and cutting powder；And second operation, remove sub-cloud from the described oil extraction liquid after separation.

Description

The processing method of used fixed abrasive wire saw cutting fluid composite

Technical field

The present invention relates to the processing method of used fixed abrasive wire saw cutting fluid composite, used fixation The renovation process of abrasive material wire saw cutting fluid composite and fixed abrasive wire saw cutting fluid composite.

Background technology

In the past, as the cutting fluid combination being used using abrasive material and when silicon ingot bar etc. being cut off using wire saw Thing it is known to containing polyether compound as oil material (with reference to patent documentation 1, patent documentation 2).

In recent years, from the viewpoint of environment reply, the raising of economy, used cutting fluid composite is given up Abandon process, attempted making its facilitation.In addition, from the viewpoint of the raising of Environmental, productivity and economy, having attempted again Using used cutting fluid composite.For example, Patent Document 3 discloses following scheme following：Will by centrifugation Abrasive material, the cutting powder decile of ingot bar are dissipated thing and are separated with cutting fluid composite, and cutting fluid composite is recycled.

On the other hand it is known that replacing free abrasive wire saw and employing fixed abrasive wire saw to cut off silicon ingot bar Deng method.Due to can make the waste material after the cutting of ingot bar, (English of the waste material after cutting is " reserve for the method Slicing ") reduce, thus have the advantages that can be effectively using ingot bar.Further, since will not mix in cutting fluid composite Enter abrasive material, thus the method can stably produce chip and not malleable cutting when the property such as the viscosity of cutting fluid composite Shape, and the cleaning of chip also becomes easy, and therefore, the method more has than the cutting-off method employing free abrasive wire saw Profit.

Prior art literature

Patent documentation

Patent documentation 1：Japanese Unexamined Patent Publication 11-286693 publication

Patent documentation 2：Japanese Unexamined Patent Publication 11-323376 publication

Patent documentation 3：Japanese Unexamined Patent Publication 01-316170 publication

Content of the invention

Invent problem to be solved

Even however, in the case of employing fixed abrasive wire saw in the cut-out of ingot bar, the cutting powder of ingot bar It is mixed in cutting fluid composite, thus in waste treatment, recycling, need described cutting powder from cutting fluid composite The operation removing.In the centrifugal separation as common removing method, even if carrying out high-speed rotation, the separation of cutting powder It is also required to the time grown very much, and separation efficiency is also poor, thus the regeneration efficiency of cutting fluid composite is low becomes problem.This class Topic becomes the obstruction that the productivity of silicon wafer improves.Even if in addition, using the technology described in patent documentation 2, cutting powder Separation property is also insufficient.Its reason be because cut powder have with the moisture in cutting fluid composite Comparatively speaking with oil The higher property of affinity.In addition, in the case of the cutting fluid composite that discarded use is crossed, such as in order to by burn processing And discarded and removed cutting powder from used cutting fluid composite it is desirable to try one's best.

The present invention provides the processing method of used fixed abrasive wire saw cutting fluid composite, and the method passes through letter Single operation, can with high separating efficiency from produced by the cut-out by ingot bar, comprise used cutting fluid composite and cut Cut Separation of Cutting powder in the oil extraction liquid of powder, the waste treatment of used cutting fluid composite becomes facilitation.In addition, this Invention provides the renovation process of used fixed abrasive wire saw cutting fluid composite, and the method passes through shirtsleeve operation, Can with high separating efficiency from above-mentioned oil extraction liquid Separation of Cutting powder, thus, it is possible to improve regeneration efficiency.In addition, the present invention carries For the fixed abrasive wire saw cutting fluid composite being fed in the enforcement of above-mentioned processing method and renovation process.

Method for solve problem

The processing method of the used fixed abrasive wire saw cutting fluid composite of the present invention is using fixing mill Material wire saw and after using in the cut-out of ingot bar that carries out, the place of used fixed abrasive wire saw cutting fluid composite Reason method, wherein,

Contained using front described fixed abrasive wire saw cutting fluid composite：

Polyethers shown in the polyether compound shown in selected from following formulas (1) of 25～75 weight % and following formula (2) At least one polyether compound (composition A) in compound,

The HLB selected from the alkyl with carbon number 12～22 of 1～9 weight % is 17.0～20.0 nonionic table At least one surfactant (composition B) in cationic surfactant shown in face activating agent and following formula (3), And

Water (composition C),

The cloud point of described fixed abrasive wire saw cutting fluid composite is 30～80 DEG C,

The processing method of described used fixed abrasive wire saw cutting fluid composite includes powder as described below Removal step：Enter from using described fixed abrasive wire saw cutting fluid composite and using described fixed abrasive wire saw Row the cut-out of ingot bar in produce, comprise used described fixed abrasive wire saw cutting fluid composite and described ingot bar Cutting powder oil extraction liquid in, at least remove described cutting powder,

Described powder removal step includes：

First operation, described oil extraction liquid is heated to the described cloud point of described fixed abrasive wire saw cutting fluid composite Above temperature, is separated into upper strata using described polyether compound as main component and based on water and described cutting powder Want the lower floor of composition, and

Second operation, from the described oil extraction liquid isolated described first operation, at least removes described lower floor,

R¹-O-(AO)_n-R^1、(1)

Wherein, in above-mentioned formula (1), R¹For carbon number 1～8 can the alkyl containing hydroxyl, R^1、For hydrogen atom or Methyl, AO are the alkylidene oxide of carbon number 2～4, n is AO average addition molal quantity and the number for expression 2～20.

Wherein, in above-mentioned formula (2), AO is the alkylidene oxide of carbon number 2～4, m1, m2 and m3 are respectively the flat of AO Equal addition molal quantity, the summation of m1, m2 and m3 are the number of expression 1～20.

Wherein, in above-mentioned formula (3), R²For the alkyl of carbon number 12～22, R³For methyl or carbon number 12～22 Alkyl, X^-Anion for 1 valency.

The renovation process of the used fixed abrasive wire saw cutting fluid composite of the present invention is to utilize fixed abrasive Wire saw and after using in the cut-out of ingot bar that carries out, the regeneration of used fixed abrasive wire saw cutting fluid composite Method,

Comprised using front described fixed abrasive wire saw cutting fluid composite：

Water (composition C),

The renovation process of described used fixed abrasive wire saw cutting fluid composite includes：

First operation, will be using described fixed abrasive wire saw cutting fluid composite and using described fixed abrasive steel Silk saw and produce in the cut-out of ingot bar that carries out, comprise used described fixed abrasive wire saw cutting fluid composite and The oil extraction liquid of the cutting powder of described ingot bar, be heated to the described cloud point of described fixed abrasive wire saw cutting fluid composite with On temperature, be separated into the upper strata with described polyether compound as main component and will be become based on water and described cutting powder The lower floor dividing,

Second operation, from the described oil extraction liquid isolated described first operation, at least removes described lower floor, and

3rd operation, to the residual liquid at least removing described lower floor and obtaining from described oil extraction liquid in described second operation In, add at least one composition in described composition A, described composition B and described composition C, obtain fixed abrasive wire saw with cutting Cut liquid compositionss.

R¹-O-(AO)_n-R^1、(1)

Invention effect

The present invention can by shirtsleeve operation with high separating efficiency Separation of Cutting powder from oil extraction liquid, thus discarded During used fixed abrasive wire saw cutting fluid composite, this waste treatment becomes easy, to used fixing mill When material wire saw is regenerated with cutting fluid composite, its regeneration efficiency uprises.

Brief description

Fig. 1 is to represent evaluation test liquid corresponding with the metewand " 7 " of Si separation property, " 5 ", " 3 ", " 1 " respectively Situation figure.

Specific embodiment

In the present invention, (below, sometimes will by used fixed abrasive wire saw cutting fluid composite will be comprised " fixed abrasive wire saw cutting fluid composite " is only called " cutting fluid composite ".) and cutting powder oil extraction liquid, be heated to The temperature more than cloud point of cutting fluid composite, thus by oil extraction liquid be separated into upper strata with polyether compound as main component, And want the lower floor of composition based on water and cutting powder, at least remove above-mentioned lower floor, thus remove from oil extraction liquid and cut powder.

In the processing method of used cutting fluid composite of the present invention and renovation process, specific contained by lower floor The amount of polyether compound is few, can carry out specific polyether compound well and separate with cutting powder.That is, in the present invention, Can with high separating efficiency from oil extraction liquid Separation of Cutting powder.And, in the present invention, cut powder and described specific polyethers Pass through using the separation method using cloud point in the separation of compound, and further using specific surfactant, thus, it is possible to Enough make cutting powder move to water layer, though do not use the such special device of centrifugal separating device it is also possible to high score from Efficiency Separation of Cutting powder from oil extraction liquid, thus be economical.Thus, if to by from oil extraction liquid at least remove sub-cloud and Residual liquid that is obtaining and comprising specific polyether compound is recycled, then can efficiency well cutting fluid composite be entered Row regeneration.In addition, in the cutting fluid composite that discarded use is crossed, by least remove sub-cloud from oil extraction liquid and can be in advance Remove water and cutting powder, for instance, it is possible to above-mentioned residual liquid, the discarded place of oil extraction liquid are easily discarded by burn processing etc. Reason becomes easy.

[fixed abrasive wire saw cutting fluid composite]

The cutting fluid composite of the present invention be the ingot bar being carried out using fixed abrasive wire saw cut-out used in cut Cut liquid compositionss, it comprises following specific polyether compounds (composition A), specific surfactant (composition B) (becomes with water Divide C), sometimes comprise the abrasive material in addition to fixed abrasive, but do not contain free abrasive in principle.

(composition A：Polyether compound)

From using fixed abrasive wire saw (hereinafter sometimes referred to simply as " wire saw ".) cut off acquisition, attachment after ingot bar There is section product, the facilitation of cleaning, the raising of the cut-out performance of wire saw of the ingot bar of cutting fluid composite and cut powder Separation efficiency improve from the viewpoint of, the cutting fluid composite of the present invention contains the polyethers shown in selected from following formulas (1) At least one polyether compound (composition A) in polyether compound shown in compound and following formula (2).

R¹-O-(AO)_n-R^1、(1)

In the case that composition A contains the polyether compound shown in formula (1), with regard to the polyether compound shown in formula (1) For, composition A can contain only a kind of polyether compound it is also possible to contain multiple polyether compounds.

From the viewpoint of the facilitation of the raising of the cut-out performance of wire saw and the cleaning of section product, described formula (1) In R¹The carbon number of (alkyl) is 1～8, from the viewpoint of identical, preferably 2～8, more preferably 3～5.In addition, from R from the viewpoint of the raising of separation efficiency of cutting powder and the low ratio foamed of cutting fluid composite, in described formula (1)¹ The carbon number of (alkyl) is preferably 1～6, more preferably 2～4.

R¹(alkyl) can be any one group in aliphatic alkyl and aromatic hydrocarbyl, from raising composition A water Dispersibility from the viewpoint of, preferred aliphat alkyl.For aliphatic alkyl, can be in saturated hydrocarbyl and unsaturated alkyl Any one group or straight-chain alkyl and branched hydrocarbyl in any one group.As R¹, such as alkane can be included Base, thiazolinyl, aryl, the especially viewpoint from the raising of separation efficiency of cutting powder and the low ratio foamed of cutting fluid composite go out Send out, preferably propyl group, isopropyl, butyl, isobutyl group, more preferably propyl group, butyl and isobutyl group, further preferred propyl group and butyl. R^1、For hydrogen atom or methyl, from raising composition A from the viewpoint of the dispersibility water, preferably hydrogen atom.

From the control of the cloud point of cutting fluid composite easily so from the viewpoint of, the AO in described formula (1) be selected from Alkylidene oxide (the oxypropylene that alkylidene oxide (oxy ethylene (EO)) that carbon number is 2, carbon number are 3 (PO) at least one) and in alkylidene oxide (oxybutylene (BO)) that carbon number is 4, from the viewpoint of identical, Preferably there is oxypropylene, more preferably only comprise oxypropylene.

From the raising of the separation efficiency of cutting powder, the facilitation of cleaning of section product, cutting fluid composite mobility Raising and cutting fluid composite low ratio foamed from the viewpoint of, n in described formula (1) is 2～20, preferably 2～16, More preferably 2～10, further preferred 2～6, still more preferably 2～4.

Polyether compound shown in described formula (1) comprises the feelings of the different alkylidene oxide of two or more carbon number Under condition, the arrangement of various alkylidene oxides can be block can also be random.In being arranged as of various alkylidene oxides In the case of block, as long as the summation of the average addition molal quantity of various alkylidene oxide is within the above range, various oxidations are sub- The block number of alkyl just can be 1 or more than 2 respectively.By wantonly a kind in alkylidene oxide of more than two kinds Alkylidene oxide constitute block number be more than 2 in the case of, the repeat number of the alkylidene oxide in each block can With mutually identical it is also possible to different.From the viewpoint of the separation efficiency improving cutting powder, poly- shown in described formula (1) Ether compound comprises oxy ethylene and oxypropylene preferably as alkylidene oxide, and oxy ethylene is sub- with oxidation Propyl group be arranged as block.For the number, the number of the block of oxypropylene of the block of oxy ethylene, as long as respectively Average addition molal quantity within the above range it is possible to respectively 1 or more than 2, but preferably 1.In addition, cutting from raising From the viewpoint of cutting the separation efficiency of powder, the polyether compound shown in described formula (1) preferably comprises oxy ethylene and makees Compound for alkylidene oxide or only comprises as the mixture of the compound of alkylidene oxide with comprising oxypropylene Oxy ethylene as alkylidene oxide compound with only to comprise oxypropylene mixed as the compound of alkylidene oxide Compound.

Polyether compound shown in described formula (1) can obtain by the following method, i.e. for example using potassium hydroxide etc. Alkali etc. as catalyst, make monohydric alcohol, phenol addition oxirane compounds and obtain.

In described formula (2), AO is the alkylidene oxide of carbon number 2～4, m1, m2 and m3 are respectively the average of AO and add Become the number that molal quantity, the summation (m1+m2+m3) of m1, m2 and m3 are expression 1～20.Contain poly- shown in formula (2) in composition A In the case of ether compound, for the polyether compound shown in regard to formula (2), composition A can contain only a kind of polyether compound, Multiple polyether compounds can also be contained.

From the viewpoint of the control of described cloud point is easy, the oxygen that the AO in described formula (2) is is 2 selected from carbon number Change alkylidene (oxy ethylene), carbon number is 3 alkylidene oxide (oxypropylene) and oxidation that carbon number is 4 At least one in alkylidene (oxybutylene), from the viewpoint of the separation efficiency of cutting powder improves, preferably aoxidizes Propylidene.

From the viewpoint of the separation efficiency improving cutting powder, the summation of m1, m2 and m3 in described formula (2) is 1 ～20, preferably 1～18, more preferably 1～12, further preferred 1～10, still more preferably 1～4.Shown in described formula (2) Polyether compound can comprise the different alkylidene oxide of two or more carbon number.

Comprise in polyether compound shown in described formula (2), average addition molal quantity is the alkylidene oxide of m1, puts down All addition molal quantity be the alkylidene oxide of m2, average addition molal quantity be m3 alkylidene oxide can identical it is also possible to not With.Addition molal quantity that comprise in polyether compound shown in described formula (2), average is the alkylidene oxide of m1, average Addition molal quantity is the alkylidene oxide of m2, average addition molal quantity be at least one in the alkylidene oxide of m3 comprise 2 kinds with In the case of the different alkylidene oxide of upper carbon number, the arrangement of various alkylidene oxides can be block or nothing Rule, the situation being more than 2 in the number of the block being made up of the wantonly a kind of alkylidene oxide in alkylidene oxide of more than two kinds Under, the repeat number of the alkylidene oxide in each block can mutually identical it is also possible to different.

Polyether compound shown in described formula (2) can obtain by the following method, i.e. for example using potassium hydroxide etc. Alkali etc., as catalyst, makes the trihydroxylic alcohol addition oxirane compounds such as glycerol, thus obtaining polyether compound.

From the raising of separation efficiency of cutting powder, the raising of the response rate of polyether compound, the cleaning of section product appearance From the viewpoint of the raising of the cut-out performance of Yi Hua and wire saw, polyether compound (composition A) in cutting fluid composite contains Measure for 25～75 weight %, preferably 30～70 weight %, more preferably 40～70 weight %, further preferred 40～60 weight %, Still more preferably 40～56 weight %.

(composition B：Surfactant)

The cleaning of section product of the ingot bar being attached with cutting fluid composite obtaining after using steel wire saw cutting ingot bar From the viewpoint of the raising of separation efficiency of facilitation, the raising of the cut-out performance of wire saw and cutting powder, the present invention cuts Cut liquid compositionss contain selected from there is the alkyl of carbon number 12～22 and HLB be 17.0～20.0 nonionic surfactant At least one surfactant (composition B) in cationic surfactant shown in agent and following formula (3).

Wherein, in formula (3), R²For the alkyl of carbon number 12～22, R³Hydrocarbon for methyl or carbon number 12～22 Base, X^-Anion for 1 valency.

In this specification, the HLB value of nonionic surfactant refers to, by Griffin method, according to HLB value=20 × The formula of (weight % of hydrophilic group) and the value that calculates.The ingot bar being attached with cutting fluid composite obtaining after cut-out ingot bar The raising of separation efficiency of the section facilitation of cleaning of product, the raising of the cut-out performance of wire saw and cutting powder sight Point sets out, and HLB is 17.0～20.0, more preferably 17.5～20.0, further preferred 18.0～20.0, even more preferably 18.2 ～19.5, still more preferably 19.0～19.5.

As nonionic surfactant, the change of the alcohol addition alkylene oxide of carbon number 12～22 of sening as an envoy to can be enumerated The ester of compound and these compounds, the alkyl that an end ether linking of ployalkylene glycol has carbon number 12～22 is made to form Compound, make two end ether linkings of ployalkylene glycol have compound of alkyl of carbon number 12～22 etc..Carbon The alkyl of atomic number 12～22 can comprise unsaturated group.

As the alkyl of the carbon number 12～22 of nonionic surfactant, obtain after cut-out ingot bar is attached with The facilitation of cleaning of section product of the ingot bar of cutting fluid composite, the raising of the cut-out performance of wire saw and cutting powder From the viewpoint of the raising of separation efficiency, alkyl, thiazolinyl, aryl can be included, carbon number preferably 16～22, more preferably carbon are former Subnumber 16～20.As alkyl, specifically, can include lauryl (dodecyl), Fancol ID base, myristyl, Palmityl, stearyl, oil base and styrenated phenol base, preferably palmityl, stearyl and oil base, more preferably stearyl and oil Base, further preferred stearyl.Nonionic surfactant can have 2 the above groups, imitates from improving to separate From the viewpoint of rate, preferably only there is 1.

Alkylene glycol used in synthesis as nonionic surfactant, it is however preferred to have carbon number is 2 Alkylidene oxide (oxy ethylene), carbon number are 3 alkylidene oxide (oxypropylene) or oxygen that carbon number is 4 Change the alkylene glycol of alkylidene (oxybutylene), from the viewpoint of the separation efficiency of cutting powder improves, preferably aoxidize Ethylidene.Composition B contain the alkyl with carbon number 12～22 and HLB be 17.0～20.0 nonionic surfactant In the case of agent, for above-mentioned nonionic surfactant, composition B can contain only a kind of nonionic surfactant, Multiple nonionic surfactants can also be contained.

Cationic surfactant shown in described formula (3) is quaternary salt type cationic surfactant, and is point There is in minor structure the compound of 1 or alkyl that 2 carbon numbers are 12～22.Alkyl is preferably saturation or undersaturated Straight or branched alkyl.R²For alkyl, from the viewpoint of the separation efficiency improving cutting powder, its carbon number is 12～ 22nd, preferably 12～20, more preferably 14～18, still more preferably 16～18.Viewpoint from the separation efficiency improving cutting powder Set out, R³For the alkyl of the alkyl of methyl or carbon number 12～22, preferred methyl or carbon number 12～20, more preferably methyl Or the alkyl of alkyl, further preferred methyl or carbon number 16～18 of carbon number 14～18, still more preferably methyl.

As the cationic surfactant shown in described formula (3), alkyl (carbon number 12～20) can be included Leptodactyline, dialkyl group (carbon number 12～20) dimethyl ammonium etc., can include such as lauryl trimethyl ammonium salt, meat Myristyl leptodactyline, palmityl leptodactyline, stearyl trimethyl ammonium salt, oil base leptodactyline, Adeps Bovis seu Bubali base front three Base ammonium salt, hydrogenated-tallow group leptodactyline, dilauryl dimethyl salt, myristyl dimethyl ammonium, two palmityls Dimethyl ammonium, distearyl dimethyl ammonium, palmityl stearyl dimethyl ammonium etc., can by these salt and with 2 kinds with On.In the middle of these, from the viewpoint of the separation efficiency improving cutting powder, preferably palmityl leptodactyline, stearyl three Methyl ammonium salt.

X^-For the anion of 1 valency, halide ions such as chloride ion, bromide ion, iodide ion etc. can be included.In the middle of these, excellent Select chloride ion, bromide ion.

From the raising of separation efficiency of cutting powder, the raising of the response rate of described polyether compound, section product cleaning Facilitation and wire saw the raising of cut-out performance from the viewpoint of, surfactant (composition B) in cutting fluid composite Content be 1～9 weight %, from the viewpoint of identical, preferably 1～7 weight %, more preferably 2～7 weight %, excellent further Select 4～7 weight %, still more preferably 4～6 weight %.In addition, the viewpoint of the operability steeping generation etc. when improving cutting Set out, the content of surfactant (composition B) is preferably 3～7 weight %, more preferably 3～6 weight %.

Polyether compound (composition A) from the viewpoint of the separation efficiency improving cutting powder, in cutting fluid composite It is preferably 6～60 with the weight ratio (composition A/ composition B) of the content of surfactant (composition B), from the viewpoint of identical, more Preferably 7～30, further preferred 8～25.

(composition C：Water)

Described cutting fluid composite contains water.Described cutting fluid composite contains water, thus cutting fluid composite have turbid Point.In addition, when being cut off using wire saw, cutting fluid composite can play cooling effect.

Water (composition C) is as long as except cutting fluid composite, polyether compound (composition A), surfactant (composition B the remainder) and beyond aftermentioned any condition, to contain, goes out from the viewpoint of the lubricity improving cutting fluid composite Send out, below content preferably 74 weight % of the water (composition C) in cutting fluid composite, below more preferably 69 weight %, enter one Below step preferably 58 weight %, below still more preferably 56 weight %.Carry from the cooling effect using cutting fluid composite From the viewpoint of the cut-out performance of high wire saw, the content of the water (composition C) in cutting fluid composite be preferably 16 weight % with More than upper, more preferably 23 weight %, more than further preferred 33 weight %, more than still more preferably 40 weight %.Thus, from From the viewpoint of the raising of the cut-out performance of the raising of the lubricity of cutting fluid composite and wire saw, in cutting fluid composite The content of water is preferably 16～74 weight %, more preferably 23～69 weight %, more preferably 23～58 weight %, more enters One step is preferably 33～56 weight %, still more preferably 40～56 weight %.

In described cutting fluid composite, contained water can be using for example, and ultra-pure water, pure water, ion exchange water or steaming are stayed Water etc., preferably uses ultra-pure water, pure water or ion exchange water, more preferably using ultra-pure water.It should be noted that pure water and super Pure water can obtain by the following method, i.e. for example tap water is passed through activated carbon, carry out ion-exchange treatment, then steamed Evaporate, the water after distillation is irradiated as needed the ultraviolet germicidal lamp of regulation, or be passed through filter, thus obtaining.For example, with regard to 25 For conductivity at DEG C, as a rule, pure water shows that below 1 μ S/cm, ultra-pure water show below 0.1 μ S/cm.

From the viewpoint of the raising of the raising of the cut-out performance of wire saw and the separation efficiency of cutting powder, described cut Cut liquid compositionss cloud point be 30～80 DEG C, preferably 32～70 DEG C, more preferably 35～65 DEG C, further preferred 35～55 DEG C, more Further preferred 37～50 DEG C, from the viewpoint of storage stability, still more preferably 40～50 DEG C.Cutting fluid composite Cloud point can be adjusted with each structure of surfactant and both containing ratios by polyether compound.

Described cutting fluid composite can contain as needed selected from hydrocarbon compound, the alkyl esters of slightly water-soluble and shipwreck The compound of more than a kind in the alkyl ketone of dissolubility is as any condition.By containing these compounds, cutting fluid composite Lubricity be improved.

As described hydrocarbon compound, can include for example, clean chip when at a temperature of for liquid, carbon number be 6～30 paraffin class straight or branched, that there is saturated bond or unsaturated bond and/or olefines, or when cleaning chip At a temperature of for the inclusion aromatic series of liquid and/or aliphatic hydrocarbon compound.

As described alkyl esters, can include for example, clean chip when at a temperature of for liquid carbon number be 6 ～40, monoesters, diester, three esters.Wherein, preferably carbon number be 6～18 higher fatty acids and carbon number be 2～8 Dihydroxylic alcohols or trihydroxylic alcohol ester；Carbon number be 1～18 higher alcohol and carbon number be 2～8 dicarboxylic acids or tricarboxylic acids Ester.

As described alkyl ketone, the preferably dialkyl ketone of carbon number 6～40.

The alkyl ketone of described hydrocarbon compound, the alkyl esters of slightly water-soluble and slightly water-soluble can be used alone, and also may be used To mix two or more use.

Described cutting fluid composite can also comprise as any condition, thickening agent, dispersant, antirust agent, chelating agen, The additives such as alkaline matter, other surfaces activating agent.

Described cutting fluid composite can comprise water miscible organic compound as the various one-tenth such as described polyether compound The medium dividing.

(preparation method of cutting fluid composite)

The preparation method of described cutting fluid composite is unrestricted, (can be become by mixing described polyether compound Point A), described surfactant (composition B) and water (composition C), remix any condition and prepared.Cut from improving preparation From the viewpoint of the operability of liquid compositionss, preferred surfactant (composition B) is mixed with water in advance and makes aqueous solution.

Described cutting fluid composite can serve as cutting off cutting fluid during ingot bar.As ingot bar, can include for producing The silicon ingot bar of silicon wafer.

(processing method of used cutting fluid composite)

The processing method of the used cutting fluid composite of the present invention is being carried out using fixed abrasive wire saw After using in the cut-out of the ingot bar, processing method of used cutting fluid composite, the method includes powder removal step：From In the cut-out of ingot bar carrying out in the cutting fluid composite using the present invention and using wire saw produce, comprise used In the oil extraction liquid of cutting powder of cutting fluid composite and ingot bar, at least remove cutting powder.Powder removal step includes first Operation and the second operation.In first operation, oil extraction liquid is heated to the temperature of more than the cloud point of cutting fluid composite, be separated into Polyether compound is the upper strata of main component and the lower floor wanting composition based on water and cutting powder.In second operation, from It is separated in one operation in 2 layers of oil extraction liquid and at least remove sub-cloud.

Here, " with polyether compound as main component " refers to, the content of the polyether compound in upper strata can than in upper strata All many with other any conditions of comprising, " wanting composition based on water and cutting powder " refers to, the content of the water in lower floor with cut The content sum cutting powder is all more than other any conditions that can comprise in lower floor.Except comprising polyether compound in upper strata Beyond (composition A), sometimes also comprise do not have helpful surfactant (composition B) to cutting powder to the movement of water layer, sometimes Also comprise the composition being not readily dissolved in water in contained any condition in the cutting fluid composite of the above-mentioned present invention, but hardly Containing water, cutting powder, preferably at least do not contain cutting powder.On the other hand, except comprising water (composition C) and cutting powder in lower floor Beyond end, sometimes also comprise the surfactant (composition B) cutting powder and moving to water layer, sometimes also comprise the present invention's Composition soluble in water in contained any condition in cutting fluid composite, also comprises a small amount of polyether compound (composition sometimes A).

For the processing method of the used cutting fluid composite of the present invention, due to being heated to than this using by oil extraction liquid Producing during the high temperature of cloud point of the cutting fluid composite of invention, polyether compound (composition A) and the segregation phenomenon of water, to enter The removing of row cutting powder it is thus possible to shirtsleeve operation and with high separating efficiency, Separation of Cutting powder from oil extraction liquid.By Produce cutting powder and be dispersed in when using fixed abrasive steel wire saw cutting ingot bar and comprise polyether compound (composition A), surface work Property agent (composition B) and water (composition C) used cutting fluid composite in, thus in such a state, cutting powder Separation efficiency is poor.However, described mixed liquor is being separated into as the upper strata of oil reservoir with as water layer by the use of cloud point phenomenon In the case of lower floor, cutting powder is comprised in lower floor, thus by removing this lower floor, and can be with high efficiency from oil extraction liquid Middle removing cuts powder.Thus, for the processing method of the used cutting fluid composite of the present invention, for example, make from oil extraction The waste treatment by burn processing etc. at least removing residual liquid obtained by sub-cloud in liquid becomes easy.Remove for from oil extraction liquid The lower floor going, for example, in the case that cutting powder is the cutting powder of silicon ingot bar, can evaporate the water and will cut powder conduct Silicon raw material is recycled.

The processing method of the used cutting fluid composite of the present invention goes for ingot bar cut-out side as described below Method：Cut off the cut off operation of ingot bar using cutting fluid composite and using fixed abrasive wire saw after, carry out using Cutting fluid composite in cutting powder removing.The cut-out of ingot bar can be carried out by the following method, i.e. by cutting fluid group Compound is supplied to wire saw and the place of incision of ingot bar or ingot bar is overall, and side makes wire saw be squeezed in ingot bar, while with a high speed Mobile traveling.

Fret saw used in cut-out for ingot bar, is not particularly limited, it is possible to use known device Come to carry out.For wire saw, also it is not particularly limited, the steel wire evidence made as follows can be included, i.e. for example pass through to be based on Nickel, the plating of copper chromium and make the abrasive material being formed by diamond, SiC adhere the piano wire with ferrum or ferroalloy as main component On, or so that it is adhered using resin bonding material.

For wire saw, for example, supplied by wire saw supply reel, wound and be arranged in and be arranged on master rotor The groove of predetermined distance on.Wire saw can make master rotor rotate and the movement that carries out advancing by the rotary speed specifying, Generally according to 400～1000m/min about mode advance at high speeds movement.It should be noted that fret saw is permissible It is the single entry carrying out cutting off processing using an one metal wire.

The oil extraction liquid producing because of cut-out ingot bar comprises used cutting fluid composite and cutting powder, for example temporary transient It is stored in the maceration tank that fret saw has.

(powder removal step)

The removing of described cutting powder includes：Described oil extraction liquid is separated into the first operation of the upper and lower；And from In the oil extraction liquid being separated into 2 layers in described first operation, remove the lower floor wanting composition based on water and described cutting powder The second operation.

(the first operation)

In first operation, first oil extraction liquid is heated to temperature (the lock out operation temperature of more than the cloud point of cutting fluid composite Degree).Before heating, can add water in advance in oil extraction liquid, adjust the content of water.Then, if oil extraction liquid is being maintained at Place in the state of lock out operation temperature or be gently mixed, then oil extraction liquid be separated into upper with polyether compound as main component Layer and the lower floor wanting composition based on water and cutting powder.In order to separate oil extraction liquid, for example, it is maintained at 1 at a temperature of lock out operation Hour.After separating oil extraction liquid, even if being also able to maintain that released state below lock out operation temperature.

The cloud point (DEG C) of cutting fluid composite be improve cutting fluid composite temperature when cutting fluid composite start white Turbid temperature.If the temperature of cutting fluid composite rises and so that the motion of hydrone is come to life, in cutting fluid composite The hydrophilic group part of polyether compound (composition A) is cut off with the hydrogen bond of hydrone, and polyether compound loses molten in water Xie Xing.Thus, if the oil extraction liquid comprising polyether compound (composition A) is heated to the temperature of more than the cloud point of cutting fluid composite After placed, then proportion is less than the polyether compound (composition A) of water and moves to the upside of water, and proportion is more than the cutting powder of water Move to downside, oil extraction liquid is separated into 2 layers.

In described first operation, from the viewpoint of the separation efficiency improving cutting powder, preferably oil extraction liquid is heated to Exceed 10～50 DEG C of temperature (lock out operation temperature) than the cloud point of cutting fluid composite, be more preferably heated to exceeding 12～50 DEG C Temperature, be further preferably heated to exceeding 20～50 DEG C of temperature, be even more preferably heated to exceeding 30～50 DEG C of temperature Spend, be still more preferably heated to exceeding 40～50 DEG C of temperature.In first operation, from the separation efficiency improving cutting powder Viewpoint is set out, and the actual temp (lock out operation temperature) of heated oil extraction liquid is preferably 40～90 DEG C, is more preferably 45～85 DEG C, more preferably 50～85 DEG C, be even more preferably 55～80 DEG C, be still more preferably 60～80 DEG C, more enter one Step is preferably 70～80 DEG C.In addition, from the viewpoint of suppressing used energy, preferably oil extraction liquid is heated to comparing cutting fluid The cloud point of compositionss exceeds 10～40 DEG C of temperature (lock out operation temperature), is more preferably heated to exceeding 10～30 DEG C of temperature, Further preferably it is heated to exceeding 12～20 DEG C of temperature.From the viewpoint of suppressing used energy, heated oil extraction The actual temp (lock out operation temperature) of liquid be preferably 40～80 DEG C, more preferably 45～80 DEG C, more preferably 45～65 ℃.

In described first operation, from the viewpoint of the separation efficiency improving cutting powder, oil extraction liquid is preferably before heating And/or be stirred in heating.

(the second operation)

In second operation, from the oil extraction liquid being separated into 2 layers the first operation, at least remove with water and cutting powder be The lower floor of main component.In the case that regeneration is carried out to upper strata, in the second operation, from the cutting fluid group that is reproduced of raising From the viewpoint of the quality of compound, preferably not only lower floor but also the part on upper strata that adjoined with lower floor are also removed from oil extraction liquid Go.For the lower floor's (comprise water and cutting powder based on want the mixed liquor of composition) removing from oil extraction liquid, can also enter again Row centrifugation, is separated into water and the beds of precipitation of cutting powder.In the case of carrying out this centrifugation, can also only remove and cut Cut the beds of precipitation of powder.For centrifugal force G (acceleration of gravity) when being centrifuged, because cutting powder is easier Precipitation, because without high centrifugal force, from the viewpoint of the operability of centrifugation, described centrifugal force G preferably 1000～ 5000G, more preferably 1000～4000G, further preferred 1000～3000G.

(reusing of residual liquid)

The side that the renovation process of the used fixed abrasive wire saw cutting fluid composite of the present invention is discussed further below Method：After using in the cut-out of the ingot bar being carried out using fixed abrasive wire saw, the present invention cutting fluid composite is entered Row regeneration.

If using the cutting fluid composite of the present invention processing method and by from the oil extraction liquid being separated into the upper and lower In at least remove sub-cloud and in the residual liquid that obtains, the concentration of polyether compound (composition A) be 25～75 weight %, surface activity The concentration of agent (composition B) is 1～9 weight %, comprises water (composition C) in residual liquid, then can be by this residual liquid directly as cutting fluid Compositionss are re-used in the cut-out of ingot bar.In the polyether compound (composition A) in residual liquid and surfactant (composition B) The concentration of one or both be the concentration outside the concentration range of above-mentioned regulation in the case of, in residual liquid add be selected from polyethers At least one composition in compound (composition A), surfactant (composition B) and water (composition C), obtains polyether compound (composition A concentration) is 25～75 weight %, the concentration of surfactant (composition B) is 1～9 weight % and comprises water, the present invention The cutting fluid composite being related to, can use it in the cut-out of ingot bar.In addition, not containing the feelings of water (composition C) in residual liquid Under condition, at least add water in residual liquid, the concentration obtaining polyether compound (composition A) is 25～75 weight %, surfactant The concentration of (composition B) is 1～9 weight % and comprises water, cutting fluid composite according to the present invention, can use it for casting In the cut-out of block.

Just adding in described residual liquid, (become selected from polyether compound (composition A), surfactant (composition B) and water Point C) in the addition of at least one composition for, measure the content of polyether compound (composition A) in residual liquid, surface activity Content of agent (composition B) and water (composition C) etc., is preferably based on this measurement result and determines above-mentioned addition.Or, can also distinguish Pre-estimate with using cutting fluid composite and cut off the cut off operation of ingot bar and described powder using fixed abrasive wire saw The decrement of polyether compound (composition A), the decrement of surfactant (composition B) and water (composition C) that removal step accompanies Decrement, will same amount of with this decrement selected from polyether compound (composition A), surfactant (composition B) and water (composition C at least one composition in) is replenished in the oil extraction liquid being obtained by forming 1 section product or multiple section product or residual liquid. The mensure of the content of composition A, composition B and composition C can use such as titration, NMR mensure, liquid chromatography etc..

The invention also discloses it is following<1>~<30>.

<1>

A kind of processing method of used fixed abrasive wire saw cutting fluid composite, it is to utilize fixed abrasive Wire saw and after using in the cut-out of ingot bar that carries out, the process of used fixed abrasive wire saw cutting fluid composite Method,

1～9 weight % selected from the alkyl with carbon number 12～22 and HLB is 17.0～20.0 nonionic table At least one surfactant (composition B) in cationic surfactant shown in face activating agent and following formula (3), And

Water (composition C),

Described powder removal step includes：

First operation, described oil extraction liquid is heated to the described cloud point of described fixed abrasive wire saw cutting fluid composite Above temperature, is separated into upper strata using described polyether compound as main component and based on water and described cutting powder Want the lower floor of composition；And

Second operation, from the described oil extraction liquid isolated described first operation, at least removes described lower floor.

R¹-O-(AO)_n-R^1‘(1)

Wherein, in above-mentioned formula (1), R¹For carbon number 1～8 can the alkyl containing hydroxyl, R^1‘For hydrogen atom or Methyl, AO are the alkylidene oxide of carbon number 2～4, n is AO average addition molal quantity and the number for expression 2～20.

<2>

According to above-mentioned<1>The processing method of described used fixed abrasive wire saw cutting fluid composite, wherein, Described ingot bar is silicon ingot bar.

<3>

According to above-mentioned<1>Or<2>The processing method of described used fixed abrasive wire saw cutting fluid composite, Wherein,

In described first operation, described oil extraction liquid is heated to 40～90 DEG C.

<4>

According to above-mentioned<1>~<3>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein,

In described first operation, described oil extraction liquid is heated to than described fixed abrasive wire saw cutting fluid composite Cloud point exceed 10～50 DEG C of temperature.

<5>

According to above-mentioned<1>~<4>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein,

In described fixed abrasive wire saw cutting fluid composite, the content of described composition C is 16～74 weight %.

<6>

According to above-mentioned<1>~<5>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein,

Described composition B is the nonionic surfactant that HLB is 18.2～19.5.

<7>

Described composition B is the nonionic surfactant that HLB is 19.0～19.5.

<8>

According to above-mentioned<1>~<7>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein,

Described composition B is that have selected from lauryl (dodecyl), Fancol ID base, myristyl, palmityl, Hard Fat The nonionic surfactant of more than a kind of alkyl in base, oil base and styrenated phenol base.

<9>

Described composition B is the cation of more than a kind in palmityl leptodactyline and stearyl trimethyl ammonium salt Surfactant.

<10>

According to above-mentioned<1>~<9>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the content of described composition B is 4～7 weight %.

<11>

According to above-mentioned<1>~<9>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the content of described composition B is 4～6 weight %.

<12>

According to above-mentioned<1>~<11>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the AO of the formula (1) of described composition A has oxypropylene.

<13>

According to above-mentioned<1>~<12>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the R of the formula (1) of described composition A¹Carbon number be 3～5.

<14>

According to above-mentioned<1>~<12>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the R of the formula (1) of described composition A¹Carbon number be 2～4.

<15>

According to above-mentioned<1>~<14>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the R of the formula (1) of described composition A^1、For hydrogen atom.

<16>

According to above-mentioned<1>~<15>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the n of the formula (1) of described composition A is 2～16.

<17>

According to above-mentioned<1>~<15>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the n of the formula (1) of described composition A is 2～6.

<18>

According to above-mentioned<1>~<11>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the AO of the formula (2) of described composition A is oxypropylene.

<19>

According to above-mentioned<1>~<18>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the summation of m1, m2 and m3 of formula (2) of described composition A is 1～12.

<20>

According to above-mentioned<1>~<19>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the content of described composition A is 40～70 weight %.

<21>

According to above-mentioned<1>~<20>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the content of described composition C is 16～74 weight %.

<22>

According to above-mentioned<1>~<20>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the content of described composition C is 23～58 weight %.

<23>

According to above-mentioned<1>~<22>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, the cloud point of described fixed abrasive wire saw cutting fluid composite is 35～65 DEG C.

<24>

According to above-mentioned<1>~<23>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, in the first operation, oil extraction liquid is heated to than described fixed abrasive wire saw cutting fluid composite Cloud point exceeds 10～50 DEG C of temperature.

<25>

According to above-mentioned<1>~<23>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, in the first operation, oil extraction liquid is heated to than described fixed abrasive wire saw cutting fluid composite Cloud point exceeds 20～50 DEG C of temperature.

<26>

According to above-mentioned<1>~<25>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, wherein, in the second operation, is centrifuged for the lower floor after removing from described oil extraction liquid.

<27>

According to above-mentioned<1>~<26>Any one of used fixed abrasive wire saw cutting fluid composite Processing method, it also includes the 3rd operation as described below：At least remove from described oil extraction liquid in described second operation In residual liquid obtained by described lower floor, add at least one composition in described composition A, described composition B and described composition C, obtain Fixed abrasive wire saw cutting fluid composite.

<28>

According to above-mentioned<27>The processing method of described used fixed abrasive wire saw cutting fluid composite, its In, in described 3rd operation, measure the content of the content of composition A, composition B and composition C in residual liquid, based on this mensure knot Really, determine addition that add in described residual liquid, at least one composition in composition A, composition B and composition C.

<29>

According to above-mentioned<27>The processing method of described used fixed abrasive wire saw cutting fluid composite, its In, in described 3rd operation, pre-estimate respectively and using fixed abrasive wire saw cutting fluid composite and using fixation Abrasive material wire saw is cutting off the decrement of the cut off operation of ingot bar and described powder removal step composition A together, the subtracting of composition B On a small quantity and composition C decrement, at least one composition in composition A, composition B and composition C is fed to oil extraction liquid or residual In liquid.

<30>

A kind of renovation process of used fixed abrasive wire saw cutting fluid composite, it is to utilize fixed abrasive Wire saw and after using in the cut-out of ingot bar that carries out, the regeneration of used fixed abrasive wire saw cutting fluid composite Method,

Water (composition C),

R¹-O-(AO)_n-R^1‘(1)

Embodiment

(preparation of cutting fluid composite)

By to coordinate according to the composition (weight %) described in table 1,2 and to mix each composition, thus obtain embodiment 1～ 22 and the cutting fluid composite of comparative example 1～13.Specifically, add water in commercially available surfactant or its aqueous solution, After adjusting surfactant and the amount of water, they are mixed with polyether compound, thus obtaining cutting fluid composite.

(mensure of cloud point)

(1) cutting fluid composite described in 50mL table 1,2 is put in the developmental tube of capacity 100mL.

(2) described developmental tube is put into water bath by side, using the bar-shaped thermometer of glass, manually to stir cutting fluid Compositionss, while make the temperature of cutting fluid composite be begun to ramp up by room temperature with the speed of 2 DEG C/min.

(3) even if becoming the temperature being stirred and after state that muddiness does not also disappear, reading cutting fluid composite.

(4) developmental tube is taken out from water bath, stir under 25 DEG C of atmosphere, and make temperature be slowly lowered to room Temperature.

(5) it is repeated twice (2)～(4), the meansigma methodss of the temperature reading using in (3) are as cloud point.

(evaluation of liquid uniformity)

(2) described developmental tube is put in the temperature chamber being adjusted to 30 DEG C, after 1 hour, visually confirm cutting fluid composite State, carries out the evaluation of liquid uniformity using following indexs.

○：Transparent

×：Nebulousurine

(3) with regard to present nebulousurine (×) cutting fluid composite for, in cutting, its oil and moisture occur to separate, right Machinability brings harmful effect.Thus, only just assume the cutting fluid composite of transparent (zero), carry out following Si separation properties Evaluate.

(mensure of Si separation property)

Si powder (the high-purity chemical of cutting fluid composite 25g and 5 μm of φ of particle diameter is put into in the plastic containers of 50mL Society's system) after 5g, then add Zr pearl (particle diameter 1mm φ, NIKKATO company system) 50g.Then, polyethylene can is installed to coating Blender (ASADA company system PC-1773) above makes it vibrate 5 hours, so that Si powder is pulverized in cutting fluid composite, by This, preparation comprises to cut with the produced Si in the Si chip cutting used for solar batteries of the reality using fixed abrasive wire saw The evaluation test liquid cutting the close Si powder of powder and cutting fluid composite is as oil extraction liquid.Now, by particle size determination machine (hole field company system, LA-920), the particle diameter confirming pulverized Si powder is about 1～1.5 μm.Then, adopted using suction hose Take 10mL evaluation test liquid to put in developmental tube, developmental tube is added a cover, makes evaluation test liquid using hot bath Temperature is warming up to the lock out operation temperature described in table 1 and table 2, keeps at such a temperature placing 1 hour.Lock out operation temperature is The temperature of evaluation test liquid, identical with the temperature of hot bath due to being considered as, thus using the temperature of hot bath as separation Operation temperature and be measured.Evaluated using index shown below and observed according to the evaluation test liquid after placing 1 hour The Si separation property arriving.In addition, Si separation property shown in Fig. 1 be 7, the example in the case of 5,3 and 1.

[metewand of Si separation property]

7：The border of upper strata and lower floor is below the 5.5mL of the scale of developmental tube

6：The border of upper strata and lower floor is the scale of developmental tube more than 5.5～6.5mL

5：The border of upper strata and lower floor is the scale of developmental tube more than 6.5～7.5mL

4：The border of upper strata and lower floor is the scale of developmental tube more than 7.5～8.5mL

3：The border of upper strata and lower floor is the scale of developmental tube more than 8.5～9.5mL

2：The border of upper strata and lower floor is the scale of developmental tube more than 9.5mL

1：The border of upper strata and lower floor is that the border of the scale that there is not developmental tube (confirms the side less than upper strata and lower floor Boundary) or inconspicuous

It should be noted that Si separation property is 7 to be optimal.Si separation property is better, then the polyether compound contained by lower floor Amount fewer.Upper strata using polyether compound as main component, lower floor using water and Si powder as main component, thus Si separate Property better, then the amount on upper strata more it may be said that at least removing the reusing of residual liquid obtained by sub-cloud from the oil extraction liquid after separation Property is better.

If the oil extraction liquid of the cutting fluid composite and cutting powder that are comprised embodiment 1～22 as shown in table 1 is heated to The temperature more than cloud point of cutting fluid composite, is separated into the upper and lower, then can by except sub-cloud with high efficiency from Cutting powder is removed in oil extraction liquid.If in addition, oil extraction liquid is separated into the upper and lower using cloud point phenomenon, can be well Carry out cutting powder to separate with described polyether compound, thus remove sub-cloud from oil extraction liquid, as a result, can return with high Yield reclaims the compositionss containing polyether compound.

Further, for the evaluation test liquid comprising embodiment 1, the cutting fluid composite of comparative example 1,2 and 6, pass through Following methods and attempt improve Si separation property.Specifically, by the developmental tube evaluated after Si separation property is installed to centrifugation point Disembark on (iuchi society CN-1040), carry out 15 minutes processing (1500G) with 4000rpm, thus attempting improving Si separation property. Based on above-mentioned [metewand of Si separation property], the Si separation property before and after centrifugation is compared.

Si separation property is that in the embodiment 1 of " 4 ", by centrifugation, Si separation property is changed into " 7 ", thus significantly improves, but It is that in the comparative example 1,2 and 6 that Si separation property is " 1 " or " 2 ", even if being centrifuged, Si separation property is also respectively " 1 ", " 2 " And " 2 ", separation property does not almost improve.

Each composition in table 1 and table 2 is as described below in detail.Polyethers in following numerals 1.～10. and table 1 and table 2 The sequence number of compound is corresponding, and the numerical value in square brackets represents weight % in the cutting agent compositionss of each composition.

Polyether compound

1. dipropylene glycol list propyl ether/i-butylene glycol 25/25]

(dipropylene glycol list propyl ether：R¹Carbon number be 3, AO=PO, n=2, Japanese emulsifying agent company system/isobutyl two Alcohol：R¹Carbon number be 4, AO=EO, n=2, Japanese emulsifying agent company system)

2.C₄O(EO)₅(PO)₄H[50]

(R¹For carbon number 4 (butyl), AO=EO and PO (block arrangement), n=9, according to following Production Example systems Make)

3. diethylene glycol [50]

(R¹Carbon number be 0, AO=EO, n=2 and light pure medicine company system)

4. hexanediol/diethylene glycol [25/25]

(hexanediol：R¹Carbon number be 6, AO=EO, n=2, Japanese emulsifying agent company system/diethylene glycol：R¹Carbon former Subnumber is 0, AO=EO, n=2 and light pure medicine company system)

5. hexanediol/diethylene glycol [15/35]

6. glycerol PO₁/ glycerol PO₁₂/ hexanediol [18.5/18.5/10.0]

(glycerol PO₁：AO=PO, m1+m2+m3=1, carry out manufacturing/glycerol PO according to following Production Examples₁₂：AO=PO, m1+ M2+m3=12, carry out manufacturing/hexanediol according to following Production Examples：R¹Carbon number be 6, AO=EO, n=2, Japanese emulsifying Agent company system)

7. glycerol PO₁/ glycerol PO₁₂/ dipropylene glycol dimethyl ether [18.5/18.5/10.0]

(glycerol PO₁：AO=PO, m1+m2+m3=1, carry out manufacturing/glycerol PO according to following Production Examples₁₂：AO=PO, m1+ M2+m3=12, carry out manufacturing/dipropylene glycol dimethyl ether according to following Production Examples：R¹Carbon number be 1, AO=PO, R^1、For Methyl, n=2, Japanese emulsifying agent company system)

8. glycerol PO₁₀[50]

(AO=PO, m1+m2+m3=10, manufactured according to following Production Examples)

9.C₄O(EO)₉(PO)₇H[70]

(R¹Carbon number be 4 (butyl), AO=EO and PO (block arrangement), n=16, carry out according to following Production Examples Manufacture)

10.C₄O(EO)₉(PO)₇H[30]

[Production Example of polyether compound]

(1)C₄O(EO)₅(PO)₄The Production Example of H

Prepare the polyether compound of the sequence number " 2 " described in table 1 by the following method.Measure its weight average by the following method Molecular weight, result is 526.

The manufacture method of the polyether compound of sequence number " 2 " is as described below.(1 rubs to add n-butyl alcohol 74.1g in autoclave You) and KOH (catalyst) 0.30g (0.4 weight %), after the air in nitrogen displacement autoclave, make height when stirring butanol Temperature in pressure kettle is warming up to 130 DEG C.In 3.5kg/cm²Pressure (gauge pressure) under will (5 moles) of oxirane 220g import high In pressure kettle, make n-butyl alcohol with reacting ethylene oxide until after described reduced pressure is extremely constant, making the temperature in autoclave be reduced to 120℃.Then, in 3.5kg/cm²Pressure (gauge pressure) under (4 moles) of expoxy propane 232g is imported in autoclaves.Make butanol With propylene oxide reaction until after described reduced pressure is extremely constant, making the temperature in autoclave be reduced to room temperature, obtaining about 520g Above-mentioned sequence number " 2 " polyether compound.

The value that the above-mentioned weight average molecular weight of the polyether compound of sequence number " 2 " is discussed further below：Under the following conditions should be based on The value being calculated with the peak in chromatograph obtained by gel permeation chromatography (GPC) method.

Post：G4000PWXL+G2500PWXL (eastern Cao's system)

Eluent：(0.2M phosphate buffer)/(CH3CN)=9/1 (Capacity Ratio)

Flow：1.0mL/min

Column temperature：40℃

Detector：RI detector

Standard substance：Polystyrene

(2) glycerol PO₁Production Example

Add glycerol 92.1g and KOH1.4g (1.5 weight %) in autoclave, carry out 30 points under 110 DEG C, 1.3kPa Clock is dehydrated.After dehydration, with the air in nitrogen displacement autoclave, after making the temperature in autoclave be warming up to 130 DEG C, add epoxy Propane 58.1g.After carrying out additive reaction and ripening at 130 DEG C, it is cooled to 80 DEG C, under 4.0kPa, removed high pressure with 30 minutes Unreacted expoxy propane in kettle.After removing unreacted expoxy propane, add acetic acid 3.0g into autoclave, at 80 DEG C After keeping 30 minutes, extracted out, obtained the PO addition product of the glycerol that average addition molal quantity is 1 mole.

(3) glycerol PO₁₂Production Example

The inventory of KOH is changed into 2.8g (3 weight %) and the inventory of expoxy propane is changed into 660.7g, in addition, Operated in the same manner as the manufacture method of the PO addition product of the glycerol being 1 mole with average addition molal quantity, obtained average addition Molal quantity is the PO addition product of 12 moles of glycerol.

(4) glycerol PO₁₀Production Example

The inventory of KOH is changed into 2.8g (3 weight %) and the inventory of expoxy propane is changed into 580.1g, in addition, Operated in the same manner as the manufacture method of the PO addition product of the glycerol being 1 mole with average addition molal quantity, obtained average addition Molal quantity is the PO addition product of 10 moles of glycerol.

(5)C₄O(EO)₉(PO)₇The Production Example of H

The inventory of oxirane is changed into 396g and the inventory of expoxy propane is changed into 406g, in addition, with C₄O (EO)₅(PO)₄The manufacture method of H is similarly operated, and the average addition molal quantity obtaining the EO of about 870g is 9 moles and PO Average addition molal quantity be 7 moles of polyether compound.Measure weight average molecular weight using said method, result is 876.

Surfactant described in table 1 and table 2 is as described below in detail.

1.EMULGEN 130K (flower king's system, the carbon number 12 (dodecyl) of alkyl, HLB=18.1)

2.SOFTANOL 500 (Japanese catalyst system, the carbon number 12 (Fancol ID base) of alkyl, HLB=18.3)

3.BLAUNON EN-1560 (blue or green wood oil fat system, the carbon number 18 (oil base) of alkyl, HLB=18.2)

4.EMANON 3119V (flower king's system, the carbon number 18 (stearyl) of alkyl, HLB=19.4)

5.BLAUNON SR-750 (blue or green wood oil fat system, the carbon number 18 (stearyl) of alkyl, HLB=17.8)

6.EMANON 3229RV (flower king's system, the carbon number 18 (stearyl) of alkyl, HLB=19.2)

7.EMULGEN A-500 (flower king's system, the carbon number 22 (styrenated phenol base) of alkyl, HLB=18.0)

8.Quartamin86W (flower king's system, R²Alkyl (palmityl, stearyl) for carbon number 16 and 18, R³For first Base, X^-For chloride ion)

9.Quartamin60W (flower king's system, R²Alkyl (palmityl) for carbon number 16, R³For methyl, X^-For chlorine from Son)

10.Quartamin24P (flower king's system, R²Alkyl (lauryl, myristyl) for carbon number 12 and 14, R³For Methyl, X^-For chloride ion)

11.Quartamin D86P (flower king's system, R²Alkyl (palmityl, stearyl) for carbon number 16 and 18, R³For The alkyl (palmityl, stearyl) of carbon number 16 and 18, X^-For chloride ion)

12.BLAUNON EH-30 (blue or green wood oil fat system, the carbon number 8 (ethylhexyl) of alkyl, HLB=18.2)

13.EMANON 1112 (flower king's system, the carbon number 12 (dodecyl) of alkyl, HLB=13.7)

14.SOFTANOL 150 (Japanese catalyst system, the carbon number 12 (Fancol ID base) of alkyl, HLB=15.3)

15.BLAUNON EN-1520A (blue or green wood oil fat system, the carbon number 18 (oil base) of alkyl, HLB=15.4)

16.BLAUNON SR-715 (blue or green wood oil fat system, the carbon number 18 (stearyl) of alkyl, HLB=13.5)

It should be noted that in table 1, " (stearyl+palmityl)/methyl " refers to, the surfactant of sequence number " 8 " is logical R in formula (3)²For stearyl, R³Surfactant for methyl and R²For palmityl, R³Mixing for the surfactant of methyl Thing.The surfactant of sequence number " 9 " is R²For palmityl, R³Surfactant for methyl.The surfactant of sequence number " 10 " is R²For lauryl, R³Surfactant for methyl and R²For myristyl, R³Mixture for the surfactant of methyl.Sequence The surfactant of number " 11 " is R²For stearyl, R³Surfactant for palmityl and R²For palmityl, R³For stearyl The mixture of surfactant.

[table 1]

[table 2]

Industrial applicability

In accordance with the invention it is possible to by shirtsleeve operation from comprising used cutting fluid composite and cutting powder With high separating efficiency Separation of Cutting powder in oil extraction liquid, thus the regeneration efficiency of cutting fluid composite is good.In addition, making discarded In the case of used cutting fluid composite, waste treatment becomes easy.Thus, the present invention can aid in the productivity of chip Raising.

Claims

1. a kind of processing method of used fixed abrasive wire saw cutting fluid composite, described compositionss have been used for profit In the cut-out of the ingot bar being carried out with fixed abrasive wire saw,

Polyethers chemical combination shown in the polyether compound shown in selected from following formulas (1) of 25～75 weight % and following formula (2) At least one polyether compound in thing be composition A,

The HLB selected from the alkyl with carbon number 12～22 of 1～9 weight % is 17.0～20.0 non-ionic surface's work At least one surfactant in cationic surfactant shown in property agent and following formula (3) be composition B and

Water is composition C,

The treating method comprises following powder removal steps：From being combined using described fixed abrasive wire saw cutting fluid Producing in thing the cut-out of ingot bar that carried out using described fixed abrasive wire saw, comprise used described fixed abrasive In the oil extraction liquid of cutting powder of wire saw cutting fluid composite and described ingot bar, at least remove described cutting powder,

Described powder removal step includes：

First operation, described oil extraction liquid is heated to more than the described cloud point of described fixed abrasive wire saw cutting fluid composite Temperature, be separated into upper strata using described polyether compound as main component and using water and described cutting powder as main The lower floor of composition, and

R¹-O-(AO)_n-R^1‘(1)

Wherein, in described formula (1), R¹For the alkyl containing hydroxyl for the carbon number 1～8 or carbon number 1～8 without hydroxyl The alkyl of base, R^1‘Be hydrogen atom or methyl, AO be the alkylidene oxide of carbon number 2～4, n be the average addition molal quantity of AO And the number for expression 2～20,

Wherein, in described formula (2), AO is the alkylidene oxide of carbon number 2～4, m1, m2 and m3 are respectively the average of AO and add Become the number that molal quantity, the summation of m1, m2 and m3 are expression 1～20,

Wherein, in described formula (3), R²For the alkyl of carbon number 12～22, R³Hydrocarbon for methyl or carbon number 12～22 Base, X^-Anion for 1 valency.

2. the processing method of used fixed abrasive wire saw cutting fluid composite according to claim 1, wherein, Described ingot bar is silicon ingot bar.

3. the processing method of used fixed abrasive wire saw cutting fluid composite according to claim 1 and 2, its In, in described first operation, described oil extraction liquid is heated to 40～90 DEG C.

4. the processing method of used fixed abrasive wire saw cutting fluid composite according to claim 1 and 2, its In, in described first operation, described oil extraction liquid is heated to the cloud point than described fixed abrasive wire saw cutting fluid composite Exceed 10～50 DEG C of temperature.

5. the processing method of used fixed abrasive wire saw cutting fluid composite according to claim 1 and 2, its In, in described fixed abrasive wire saw cutting fluid composite, the content of described composition C is 16～74 weight %.

6. the processing method of used fixed abrasive wire saw cutting fluid composite according to claim 1 and 2, its In, described composition B is the nonionic surfactant that HLB is 18.2～19.5.

7. the processing method of used fixed abrasive wire saw cutting fluid composite according to claim 1 and 2, its In, described composition B is the nonionic surfactant that HLB is 19.0～19.5.

8. the processing method of used fixed abrasive wire saw cutting fluid composite according to claim 1 and 2, its In, described composition B is dodecyl, Fancol ID base, myristyl, palmityl, stearyl, oil for having selected from lauryl The nonionic surfactant of more than a kind of alkyl in base and styrenated phenol base.

9. the processing method of used fixed abrasive wire saw cutting fluid composite according to claim 1 and 2, its In, described composition B is that the cationic surface of more than a kind in palmityl leptodactyline and stearyl trimethyl ammonium salt is lived Property agent.

10. the processing method of used fixed abrasive wire saw cutting fluid composite according to claim 1 and 2, Wherein, the content of described composition B is 4～7 weight %.

The processing method of 11. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, the content of described composition B is 4～6 weight %.

The processing method of 12. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, the AO of the formula (1) of described composition A has oxypropylene.

The processing method of 13. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, the R of the formula (1) of described composition A¹Carbon number be 3～5.

The processing method of 14. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, the R of the formula (1) of described composition A¹Carbon number be 2～4.

The processing method of 15. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, the R of the formula (1) of described composition A^1‘For hydrogen atom or methyl.

The processing method of 16. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, the n of the formula (1) of described composition A is 2～16.

The processing method of 17. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, the n of the formula (1) of described composition A is 2～6.

The processing method of 18. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, the AO of the formula (2) of described composition A is oxypropylene.

The processing method of 19. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, the summation of m1, m2 and m3 of formula (2) of described composition A is 1～12.

The processing method of 20. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein,

The content of described composition A is 40～70 weight %.

The processing method of 21. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, the content of described composition C is 23～58 weight %.

The processing method of 22. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, the cloud point of described fixed abrasive wire saw cutting fluid composite is 35～65 DEG C.

The processing method of 23. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, in the first operation, oil extraction liquid is heated to exceeding 20～50 DEG C of temperature than the cloud point of cutting fluid composite.

The processing method of 24. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, Wherein, in the second operation, the lower floor removing from described oil extraction liquid is centrifuged.

The processing method of 25. used fixed abrasive wire saw cutting fluid composites according to claim 1 and 2, It also includes the 3rd following operations：At least remove obtained by described lower floor from described oil extraction liquid in described second operation In residual liquid, add at least one composition in described composition A, described composition B and described composition C, obtain fixed abrasive wire saw Use cutting fluid composite.

The processing method of 26. used fixed abrasive wire saw cutting fluid composites according to claim 25, its In, in described 3rd operation, measure the content of the content of composition A, composition B and composition C in residual liquid, based on this mensure knot Really, determine addition that add in described residual liquid, at least one composition in composition A, composition B and composition C.

The processing method of 27. used fixed abrasive wire saw cutting fluid composites according to claim 25, its In, in described 3rd operation, pre-estimate respectively and using fixed abrasive wire saw cutting fluid composite and using fixation Abrasive material wire saw is cutting off the decrement of the cut off operation of ingot bar and described powder removal step composition A together, the subtracting of composition B On a small quantity and composition C decrement, then by least one composition in composition A, composition B and composition C be fed to oil extraction liquid or In residual liquid.

A kind of 28. renovation process of used fixed abrasive wire saw cutting fluid composite, described compositionss have been used for In the cut-out of the ingot bar being carried out using fixed abrasive wire saw,

Water is composition C,

Described renovation process includes：

First operation, will be using described fixed abrasive wire saw cutting fluid composite and using described fixed abrasive wire saw And in the cut-out of the ingot bar carrying out produce, comprise used described fixed abrasive wire saw cutting fluid composite and described The oil extraction liquid of the cutting powder of ingot bar, is heated to more than the described cloud point of described fixed abrasive wire saw cutting fluid composite Temperature, is separated into the upper strata using described polyether compound as main component and using water and described cutting powder as mainly becoming The lower floor dividing,

3rd operation, in the residual liquid at least removing described lower floor and obtaining from described oil extraction liquid in described second operation, Add at least one composition in described composition A, described composition B and described composition C, obtain the cutting of fixed abrasive wire saw Liquid compositionss,

R¹-O-(AO)_n-R^1‘(1)